MXPA98004524A - Rocio composition for hair which has 80% or less of volatile organic compounds and physical characteristics and performance - Google Patents

Abstract

The present invention relates to a hair spray composition with 80% or less of VOCs (volatile organic compounds), which includes a fixative which is the half ester of a copolymer of maleic anhydride and methyl vinyl ether, which has advantageous physical and of performance even with very low levels of fixative. The copolymer is prepared by polymerizing the monomers at a selected temperature in the presence of a predetermined amount of a polymerization initiator whose decomposition fragments are soluble in hydroalcoholic solutions containing high levels of water. The composition is transparent and does not form precipitates, has a low average molecular weight and a narrow molecular weight distribution, or polydispersity, thus obtaining a low viscosity solution. The composition also forms a small particle size spray pattern, obtaining transparent films, hard fixation, with a better adhesion to the user's hair, an advantageous retention of the curl in high humidity (maintenance) and a short time of stickiness and drying, both in spray products with pump or atomizer and in aerosol products

Description

COMPOSITION OF SPRAY FOR HAIR WHICH HAS 80% OR LESS VOLATILE ORGANIC COMPOUNDS AND PHYSICAL CHARACTERISTICS AND ADVANTAGING PERFORMANCE BACKGROUND OF THE INVENTION FIELD OF THE INVENTION The present invention relates to hair spray compositions and more particularly to hair spray compositions having 80% or less of volatile organic compounds (VOC), which have advantageous physical and performance characteristics. DESCRIPTION OF THE PREVIOUS TECHNIQUE The copolymers of alelic anhydride and methyl vinyl ether in the form of alkyl halides of 1 to 5 carbon atoms, for example the ethyl ester, have been used extensively as film-forming resins or fixatives in spray compositions for The hair. In general, such ester copolymers have been prepared by the polymerization of a benzene or acetone solution of the monomers in the presence of a free radical polymerization initiator, followed by an esterification. See British Patents No. 863,379; 1,233,468 and 712,220; German Patent No. 540,101 and US Patents U.S. 2,047,398; REF: 27556 4,908,413; 4,939,198; 5,139,034 and 5,223,567. In general, the free radical initiators used in these polymerization processes at elevated temperatures include alkyl peresters, dialkyl peroxides, perketals, peroxydicarbonates, hydroperoxides, azo compounds and labile carbon-carbon compounds. The copolymerization can also be carried out at relatively low temperatures, for example at room temperature, using a redox catalyst, such as a combination of a redox catalyst and ascorbic acid, or of peroxydicarbonate and benzoin. It has also been possible to use the polymerization initiator in conjunction with a suitable accelerator, for example, an amine derived from a cyclic structure or phenyl, wherein the amine is used alone or together with an organic compound of a transition metal. The copolymerization has also been carried out with a mixture of different polymerization initiators having different decomposition temperatures. The following compounds have been used as initiators in polymerizations initiated by free radicals: acetylcyclohexanesulfonyl peroxide, diacetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, tert-butyl per [oxy] -neodecanoate, 2,2 ' -azobis (4-methoxy-2, -dimethylvaleronitrile); tert-butyl peroxide pivalate, dioctanoyl peroxide, dilauroyl peroxide, 2,2'-azobis (2,4-dimethylvaleronitrile), tert-butylazo-2-cyanobutane; dibenzoyl peroxide, tert-butylper [oxy] -2-ethylhexanoate, tert-butylper [oxy] -maieate, 2,2-azobis (isobutyronitrile); bis (tert-butylperoxy) cyclohexane, tert-butylperoxyisopropyl carbonate, tert-butylper [oxy] acetate; 2, 2-bis (tert-butylperoxy) utane, dicumyl peroxide, ditert-amyl peroxide, ditert-butyl peroxide, pineane hydroperoxide, cumene hydroperoxide, and tert-butyl hydroperoxide. The ethyl hemiesters of the maleic anhydride and methyl vinyl ether copolymers (Gantrez® ES-225) can be prepared in acetone according to a free radical polymerization process described by Zamora et al. , in the U.S. Patent 5,223,567; using decanoyl peroxide as the polymerization initiator. Such copolymers are supplied by International Specialty Products, Inc. in the form of a solution with 50% solids in ethanol. However, recent government legislation has requested that hair spray compositions contain only 80% or less of volatile organic compounds (VOC). Accordingly, it has been necessary that the formulations of such hair sprays replace with water a part of the ethanol which is used as a solvent to dissolve the hair setting resin. However, an increase in water content creates some significant problems, including: A decrease in the solubility of the resin. An increase in the viscosity of the solution. An increase in the size of sprayed particles, causing a poor spray pattern. An increase in drying and tack time.

A decrease in the resistance of the curl to high humidity (maintenance). In aerosol formulations, the presence of water creates two additional problems: - Corrosion of the can. Incompatibility with the propellant solvent. Specifically, in a formulation with low VOC and particularly in a composition with 55% VOC having a very high water content, Gantrez® ES-225 only forms turbid compositions with a high viscosity of the solution. These appearance properties are commercially unacceptable because of the opaque appearance of the product and the formation of a precipitate over time. In addition, such high viscosity formulations are difficult to spray properly in fine particle spray patterns. Accordingly, Gantrez® ES-225 has not been considered as a suitable candidate as a fixative for a hair spray product with 55% VOC. Goertz et al. , in the U.S. Patent 4,908,413, described the preparation of ethyl ester anhydride maleic anhydride copolymers and an excess of methylvinyl ether by a thermal polymerization of the pre-charged monomers in acetone, followed by a second phase of free radical polymerization. The esterification was carried out in ethanol in the presence of an esterification catalyst such as p-toluenesulfonic acid. However, the alcoholic solutions of such copolymers were considered only "equivalent in their physical properties and performance characteristics to the corresponding ones obtained by the above processes". For these and other reasons, there has been extensive research and development, both in the chemical industry and in cosmetics, to find new polymers and / or polymer blends that provide hair spray compositions with 80 and 55% acceptable VOCs for the consumer. Accordingly, an object of the present invention is to provide a hair spray composition with 80% or less of VOC, particularly a composition with 55% VOC, that exhibits excellent performance properties, even at a low level of fixing solids and that it is a clear fixative solution, without formation of precipitates and having a low viscosity of solution, a low average molecular weight of copolymers and a narrow molecular weight distribution (MWD) and that also forms a spray pattern of small particle size, forming clear films and hard fixation, with a superior adhesion to the user's hair and providing an effective retention of the curl with high humidity (maintenance), as well as a low time of stickiness and drying, both in products of spray for the hair with pump or atomizer as in aerosol products. These and other objects and features of the present invention will be apparent from the following detailed description of the invention. BRIEF DESCRIPTION OF THE INVENTION What is described herein is a hair spray composition containing 80% or less of VOC, which comprises, by weight, a) from about 0.5 to 12% ethyl ester copolymer or maleic anhydride butyl and methyl vinyl ether, which is prepared by copolymerizing the monomers in a solvent at a predetermined temperature, in the presence of a selected amount of a polymerization initiator whose decomposition fragments in the solution are soluble in a composition hydroalcoholic with 55% VOC, followed by esterification, preferably in the absence of an esterification catalyst and wherein the copolymer solution is transparent, has a low average molecular weight of from about 30,000 to about 120,000, preferably from 50,000 to 100,000 and more preferably from 60,000 to 80,000, a narrow polydispersity or molecular weight distribution (MWD) less than about 2.5, preferably from 1.8 to 2.2, and a specific solution viscosity of about 0.25 to 0.39, preferably from 0.28 to 0.35, i) optionally neutralized in an amount of up to about 25 mole percent, b) from 0 to 80% ethanol, c) from 19 to 99% water and d) from 0 to 35% of propellant The hair spray composition of the present invention has a transparent appearance, has a Brookfield viscosity of less than 30 cps, preferably less than 20 cps, in the form of a solution with 5% solids, and forms transparent and hard films having a retention of curling at high humidity (maintenance) greater than 90%, a tack time of less than 30 seconds, a drying time of less than 45 seconds and forms dew particles in pump or atomizer systems that are smaller than 100 μm and, in aerosol systems , less than 80 μm. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the manufacture of alkyl halides of maleic anhydride and methyl or butyl vinyl ether in accordance with Zamora, using decanoyl peroxide as the polymerization initiator, causing the formation of decomposition fragments of the initiator. which remain in the copolymer solution and are insoluble in water. Accordingly, it is these fragments of initiator decomposition which cause hydroalcolic solutions and hair spray compositions containing water having 80% or less of VOC, particularly 55% or less of VOC and containing such solutions of commercial copolymer, have an opaque and hazy appearance and still form a precipitate with time. In contrast, it has been found that the hemiester copolymer itself is readily soluble in compositions with 80% VOC or 55% VOC. Such solutions have a transparent appearance. In accordance with the above, hydrocompatible copolymers and solutions thereof are prepared in the present invention using polymerization initiators whose decomposition fragments are - in ¬ compatible with hydroalcoholic solutions with 80% or 55% VOC. Suitable initiators include azobis-type compounds having a solubility of 0.5 g of initiator / 100 g of water. These compounds may be present during the polymerization in an amount from about 0.05 to about 10% by weight of the monomers used, preferably from about 1 to about 5%. Representative azo initiators for use herein include: 1,1'-azobis (1-cyclohexanecarbonitrile); 2,2'-azobis dihydrochloride (N, '-dimethylenisobutylamidine); 2, 2'-azobis (2-amidinopropane) dihydrochloride; - 2, 2'-azobis (N, N'-dimethylenisobutyramidine); 4, 4'-azobis (4-cyanopentanoic acid); 2,2 '-azobis. { 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide); 2,2'-azobis'2-methyl-N- [l, 1- bis (hydroxymethyl) ethyl] proponamide}; 2, 2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide; and 2,2'-azob? s dsobutyral ida dihydrate). Other azo initiators can also be used which have a solubility in water of less than 0.5 g / 100 g of water but whose decomposition products are suitably soluble in hydroalcoholic solutions. Such azo initiators include: 2,2'-azobis (isobutyronitrile); 2, 2 'azobis (2,4-dimethylvaleronitrile); - 2, 2 'azobis (4-methoxy-2,4-dimethylvaleronitrile); 1, 1'-azobis (1-cyclohexanecarbonitrile); and dimethyl-2, 2'-azobis (isobutyrate). The copolymers prepared using the appropriate azo initiators and their hair spray solutions and compositions have advantageous physical and performance properties compared to copolymer and hair spray compositions prepared either by the processes of Zamora or those of Goertz. In particular, the copolymers of the present invention have a low average molecular weight and a narrow polydispersity or molecular weight distribution, which produces hair spray compositions having a desirable low viscosity suitable to form dew-particles advantageously of small size , both in pump or atomizer systems and in aerosol systems. With these solutions and copolymer compositions, the consumer can experience exceptional maintenance power on the hair, while at the same time having time acceptable tackiness and drying. In the present invention, the average molecular weight and polydispersity of the copolymer can be controlled using a predetermined amount of the azo initiator during the polymerization and by selecting a suitable polymerization temperature. For example, for a selected low average molecular weight of about 50,000 to 80,000, and a polydispersity of about 1.8 to 2.2, a suitable amount of azo initiator having a median life of 10 hours of about 60 to 70 ° C, is about 1 to about 5% by weight of the maleic anhydride monomer present during the polymerization, and the polymerization temperature is from about 60 to about 90 ° C. In addition, the advantageous physical and performance properties of the hemiester copolymer of the present invention in the hair spray compositions is increased by carrying out the polymerization step solely by free radical polymerization, which reduces the average molecular weight of the copolymer. Preferably, the esterification is carried out in the absence of an esterification catalyst. Such acid catalysts remain the resulting ester copolymer solution and produce an opaque film when obtained from high water content hydroalcoholic solutions. In addition, the presence of an esterification catalyst will produce significant amounts of the diester copolymer, which is undesirable because it is less compatible with water than the hemiester copolymer. The diester also has a reduced Tg such that the fixing film is softer than that of the hemiester copolymer of the present invention. If desired, the hemi ester copolymer solution herein can be neutralized to about 25 mol% with a suitable neutralizing agent, such as triisopropanolamine (TIPA), 3-aminopropanol (AMP-95) NH 4 OH or NaOH and the like. In general, a higher degree of neutralization will be used in a hair spray composition having a high water content. The present invention will now be described in more detail with reference to the following Examples. EXAMPLE 1 (INVENTION) PREPARATION OF THE ETILESTER OF A COPOLYMER OF MALYLIC ANHYDRIDE-METHYLLELL ETHER, IN ETHANOL (a) Copolymerization A pressurized reactor was precharged with 7819 pounds of acetone and maintained at 70-80 ° C with stirring under a nitrogen atmosphere. Then, 5225-pound currents of molten maleic anhydride (MA), 3713 pounds of methylvinyl ether, were introduced separately.

(MVE) liquid and a solution of 209 pounds of 4,4'-azobis (4-cyanopentanoic acid) in 1033 pounds of acetone (4% by weight based on the MA) and continuously to the pre-charged reactor. The rate of addition of MA was 15.47 pounds / min; the MVE addition rate was 21.77 lbs / min and the rate of addition of the initiator solution was 5.18 lbs / min. The addition period was 6 hours. The product was a transparent, odorless, viscous solution with 50% solids in acetone, of the maleic anhydride-methyl vinyl ether copolymer having a specific viscosity of about 0.3 and less. There was a substantial absence of residual monomers, acetone and maleic acid in the solution. (b) Esterification and (c) Exchanging Solvents The solution of the copolymer (in acetone) was subsequently esterified and the solvent exchanged by ethanol by injection of vaporized methanol at a temperature of 85 to 95 ° C continuously through of bubbling tubes below the surface of the solution, over a period of 8 hours while the acetone was simultaneously distilled at atmospheric pressure to the boiling point of the solution (about 60 ° C). The product was a clear, odorless solution in ethanol, the ethyl ester half ester of the copolymer, with a solids content of 50%, with less than 0.2% acetone and substantially no residual monomers or maleic acid, at a specific viscosity of about 0.4. or less. COMPARATIVE EXAMPLES EXAMPLE 2 (ZAMORA) Example 1 of US Pat. No. 5,233,367 to Zamora (in which decanoyl peroxide was used as the polymerization initiator), was repeated to obtain the ethyl ester copolymer of maleic anhydride and methylvinyl ether in the form of a 50% solution in ethanol. A hair spray composition with 55% VOC was prepared using this copolymer solution, and its properties were determined in a comparative test with similar hair spray compositions containing the copolymer solution of the present invention. EXAMPLE 3 (GOERTZ) Example 1 of US Pat. No. 4,908,413 by Goertz (in which 2, 2'-azobis (2, -dimethylvaleronitrile) was used as the polymerization initiator and p-toluenesulfonic acid as a catalyst of the invention. esterification), to obtain a copolymer of maleic anhydride ester and methyl vinyl ether in the form of a 50% solution in ethanol. A hair spray composition with 55% VOC was then prepared using this copolymer solution and its properties were determined in comparative tests with the composition of the present invention. COMPOSITIONS OF THE INVENTION Various compositions were prepared with pump or atomizer system and with aerosol system with the components of the present invention and are shown in Table 1. TABLE 1 DEVICE COMPOSITIONS FOR HAIR WITH 55% VOC OF THE INVENTION Pump System or atomizer * Components% In Weight (A) (B) Copolymer of Example 1 4.0 4.0 (at 100% solids) AMP-95 - 0.18 TIPA 0.38 Ethanol (total) 55.0 55.0 Water 40.62 40.82 pH 5.40 5.55 * Seaquist Euromist II (output 160 mcl) with actuator 0.018"X 0.010".

Aerosol System ** (A ') (B') Copolymer of Example 1 5.0 5.0 (at 100% solids) AMP-95 0.23 0.23 Ethanol (total) 20.0 20.0 Agu-, 39.17 8.92 Corrosion inhibitors Liquid phase (MEA-Borate and 0.40 0.40 MIPA-Borate Menacore® BE) Steam phase (NH4OH) 0.20 0.20 DME propellant (dimethyl ether) 35.00 HFC-152A (duPont) 30.00 (A) (B) ** Seaquist valve ST-74 ** Seaquist ST-174 0.018 X Valve Cover X 0.015 VT 0.013 X 0.062 Std. X No X 0.050 DI VT X 0.122 DI Actuator: ST-150 Misty Actuator: ST-200 Misty Orifice: 0.023"Orifice: 0.018" pH (of the concentrate, without 6.5 6.6 propellant) In spray formulations with a high solids content, for example at 10-12% solids, a Appropriate spray using an appropriate spray equipment, as follows: For aerosols: a Seaquist ST-74 valve system with 0.010"neck / cover body / 0.010" VT / 0.030"DI; Actuator: ST-150 Misty, 0.020 hole " spray index: 0.25"-0.28" Pattern: 3-1 / 2-4"PROPERTIES OF THE COPOLYMERS OF THE INVENTION Table 2 summarizes the average molecular weight, polydispersity and specific viscosities for the various Examples. In Table 2, the present invention possesses the lowest average molecular weights and specific viscosity values, ie, 63,900 and 0.28, respectively, compared to the other Examples.The present invention also possesses the narrowest polydispersity, being this 2.0.

TABLE 2 PHYSICAL PROPERTIES OF THE COPOLYMERS OF THE INVENTION AND COMPARATIVE COPOLYMERS Copolymer Molecular peptide Polydispersity, Average viscosity Mw / Mn specifies ** Wt, * M * H VO Invention (Example 1 63,900 2.0 0.28 Zamora (Example 2 82,700 3.2 0.35 Goertz (Example 3 160,000 3.2 0.99 * Based on the polystyrene calibration curve. ** 1% by weight solution in ethanol.

Table 3 presents the performance characteristics for the user of hair spray compositions with 55% VOC and pump system or atomizer containing (A) the Gantrez® ES-225 copolymer in ethanol, wherein the copolymers are prepared in accordance with (B) Zamora or (C) Goertz, in comparison with (D) the present invention. As shown herein, the lower average molecular weight and narrow polydispersity of the copolymers of the present invention provide performance attributes in the respective formulations that are superior to solutions containing copolymers of Gantrez® ES-225 or of Zamora or Goertz. The low specific viscosity of the formulations using the copolymer of the present invention also reduces the tack time and the drying time of the system, and furthermore provides a very desirable spray pattern.

TABLE 3 COMPARISON OF PERFORMANCE OF DEBRIS COMPOSITIONS FOR HAIR WITH 55% VOC AND PUMP SYSTEM, FOR THE USER (A) (B) (C) (D) Gantrez® ES-225 Zamora Goertz Invention * (100% VOC) ) (55% VOC) (55% VOC) (55% VOC)% Active (5.5% solids 4.0% 4.0% 4.0% polymer) Film hardness 3H-4H 6H 9H 5H (70F / 50% RH) 9H = very hard IB = very soft Clarity of the film Transparent Opaque Opaque Transp. (70F / 50% RH) 1 HHCR (Maintenance) 95.35% 98.03% 96.06 98.52 t H (80F / 90% RH) @ 90 minutes 1 HHCR 92.61% 96.03% 94.60% 96.15% (80F / 90% RH) @ 4 hours Duration of 18 sec 42 sec 36 sec 23 sec tackiness Drying time 39 sec 54 sec 65 sec 44 sec * Copolymer is 10% neutralized TABLE 3 (continued) COMPARISON OF SPRAY COMPOSITION PERFORMANCE FOR HAIR WITH 55% VOC AND PUMP SYSTEM, FOR THE USER (A) CB) (C) (D) Gantrez * ES-225 Zamora Goertz Invention * (100% VOC) (55% VOC) (55% VOC) ) (55% VOC) Rigidity 7.6 8.0 8 10 = very very stiff 1 = very very soft Formation of flakes 9.2 7.2 8.6 10 = no flakes 1 = very covered with flakes Ease of combing 6.8 6.6 8.6 6.2 10 = no drag If 1 = very heavy drag 1 Removal Acceptable Acceptable Acceptable Acceptable Particle Size 80 micron 105 micron 143 micron 83 micron D [v, 0.5) Spray pattern 6 6"2.5-3" 3 1 / 2-4 3 1/2"3.5" Spray character Fine spray Spray Coarse spray Fine coarse spray Fine initial curl drop 6% 28% 10% 7% (70F / 50% RH) ß 10 minutes PUMP: Seaquist Euromist II (160 mcl outlet) with 0.018"X 0.010" actuator.

More particularly, as shown in Table 3 above, the compositions of the present invention (D) provide clear hair spray compositions, with maintenance of > 90%, a tack time of < 30 seconds, a drying time < 45 seconds, and a particle size in the pump or atomizer <100 μm, in the form of fine particles. In contrast, the Zamora hair spray compositions (B) are opaque, provide less than 90% maintenance, a tack time greater than 40 seconds, a drying time greater than 60 seconds and thicker dew particles greater than 100 μm in size. The hair spray compositions prepared using the Goertz copolymer solution (C) also had a little opacity, a prolonged sticking time of 36 seconds, a very long drying time of 65 seconds and a particle size 143 μm, thick appearance. Accordingly, the copolymer solutions of the present invention and the hair spray compositions with 55% VOC with which they were prepared, exhibit physical and performance characteristics that are commercially acceptable, while the copolymer solutions of Gantrez® ES-225 and copolymer solutions from Zamora and Goertz provide much less acceptable products. In Table 3 it can also be seen that the present invention provides an initial drop of desirably low curl, of 7%, in formulations with 55% VOC, which is comparable with anhydrous systems, while the formulations using Zamora copolymers and Goertz gave initial ripple fall values of 28 and 10%, respectively. As described, the decanoyl peroxide initiator residues are responsible for the unacceptable opacity / precipitate in the formulations using the Zamora copolymer containing a high percentage of water. These initiator residues, for example ethyl decanoate, also appear to plasticize the copolymer and could contribute to the prolonged stickiness and drying times observed, with the softness of the films and the high initial drop value of the curl for the spray compositions for the hair containing such copolymer solutions. A similar study of aerosol compositions is presented in Table 4. The results are parallel to those obtained with pump or atomizer systems.

TABLE 4 COMPARATIVE COMPOSITIONS OF SPRAY FOR HAIR SPRAY (A) (B) (B ') Gantrez® ES-225 Copolymer Copolymer (100% VOC, 4% Invention Active Invention) 35% DME 30% 152a ( 55% VOC, 5% Active) (55% VOC, 5% Active) Film Hardness 9H 9H 9H (70F / 50% RH) 9H = Very hard IB = Very soft Clarity of the film Transp, Transp. Transp. (70F / 50% RH) HHCR,% 100 98.81 100 NJ (80F / 90% RH) @ 90 minutes HHCR,% 84.39 89.32 98.75 (80F / 90% RH) @ 4 hours Stick duration49.8 13.0 20.8 dad, sec . Drying time 65.6 22.0 33.2 TABLE 4 (COHTIMUACIOII) (A) (B) < B ') Rigidity 8.4 7.2 9H 10 = Very very stiff 1 = Very very soft Formation of flakes 8.8 8.8 10 = No flakes 1 = Very covered in flakes Ease of Combing 6.8 8.0 100 10 = No drag 1 = Very heavy drag Removal Acceptable Fair Acceptable Particle size 97 microns 38 microns 69 microns Dlv, 0.5) Spray pattern, (-> 6"4" 4"4.5" Spray character Very fine spraying Fine spraying Fine spray Spray index 0.54 0.60 0.90 (grams / sec ) Valve / actuator Seaquist ST-74 0.018 x Seaquist ST-71 0.013 capillarity X x 0.062 Std. 0.015 VT x 0.050 ID NO VT x 0.122 DI ST-150 Misty 0.023"ST-200 Misty 0.018 ' The copolymer solutions of the present invention can utilize 80% VOC, as disclosed. COMPOSITIONS OF THE INVE Film clarity Film hardness acceptable pH HHCR long-term - 90 min. HHCR * e long-term-4 hrs Drying (time of) 46.4 46.0 Stickiness (duration) 32.8 33.0 Rigidity 6.8 6.0 Hairstyle 7.6 8.0 Hair 9.2 8.8 Brightness 9.2 9.6 Combinability 7.6 7.4 Curly 8.4 7.0 Manageability 6.2 3.4 In summary, the low viscosities of the solution of the hair spray compositions containing the copolymer solution of the present invention, improves the spray characteristics of the hair spray formulation, obtaining an excellent particle size and causing better stickiness and drying times. Such formulations, even at very low solution viscosities, also show excellent hair maintenance under normal conditions of use. The close polydispersity of the copolymers of the present invention also maximizes the use of an optimized average molecular weight for better maintenance property, while minimizing the amount of low molecular weight fractions, which could plasticize the film and reduce the maintenance. The substantial absence of high molecular weight fractions in the copolymer of the present invention is also advantageous, because such fractions produce undesirable viscosity fluxes and negatively affect the aesthetics of the spray. In addition, the low viscosity of the high solids formulations of the copolymer solutions herein provide a more rigid maintenance characteristic for the user. APPENDIX The following test protocols were used here; other properties and performance characteristics were obtained by standardized test procedures. 1. SOLUBILITY To determine if the copolymers and polymer solutions were soluble in ethanol / water solutions with 80% VOC or less, the following procedure was used. PROCEDURE: 1. A hair spray formulation with 80% VOC or less is prepared with the "test" copolymer. 2. The copolymer is neutralized as necessary with a base. 3. The finished prototype is visually examined and the test solution is scored as follows: Rating: Transparent - Completely soluble polymer. Opaque - Polymer dissolved, but the solution looks opaque. Insol / PPT - The polymer is not soluble and precipitates. 2. RETAINING RETENTION AT HIGH HUMIDITY The retention properties of the styling curl of the finished products containing resins were measured at 80 ± 2 F / 90 ± 2% RH in a specified period. The change in curl retention percentage versus time was plotted to illustrate the differences between the various formulations. EQUIPMENT: - Duco Cement European brown hair 8"Scissors Nylon comb Plexiglass frames cut to 1" - 2-7 / 8"x 5/8" curling iron and 5/8"metal clamps Shampoo of .plexiglass and retainer boards with 1/4"marks Environmental chamber (with precision of ± 2% RH and 80 ± 2 F) shampoo PROCEDURE: A. Preparation of Hair Sample Cuts 1. Hair is separated in cuts of 2 grams of weight 2. The roots are stuck on a plexiglass box of 1". The glue is allowed to dry completely.

It combs to remove excess hair. Each haircut is cut so that it measures 6.5"in length from the bottom of the plexiglass square to the root.Make sure that all the strands used have the same length.

The initial length will be referred to as Lo. Wash the strands of hair with a 10% shampoo solution (reviving, lite or EFA shampoos are acceptable, but make sure the same shampoo is used in all tests). The locks are rinsed well with hot running water. He combs to untangle the strands. Preparation and Exposure of Test Samples Excess water is squeezed by pressing the strands between the thumb and forefinger and running down. Note: The tufts should be prepared one day before the test and can not be used if they were kept rolled more than 24 hours. Check the conditions of the camera (80 ± 2 F / 90 ± 2% RH). Adjust as necessary and allow the camera to equilibrate before preparing the strands for testing. * Verify (Section C) the application of the products before curling the hair. 10. Curl the hair in a cairel configuration by rolling it diagonally over a curling iron. /8"The hair is secured on the curling iron with a metal pin 11. The hair is dried on the curling iron at room temperature overnight on a horizontal surface or suspended on hooks for drying for 1 hour, except for gel and mousse.The curls treated with gel or mousse should be dried in an oven set at 100 ° C for 1 hour and then dried at room temperature overnight on a horizontal surface 12. The next day the pin is carefully removed and slide the curler to remove it from the hair 13. The curly strand is suspended in the plexiglass and a controlled amount of product is applied in the manner that will be described later 14. The treated curls are allowed to rest on a horizontal surface and are left air dry for 1/2 hour, except for gels and mousse 15. Dried treated curls are suspended randomly on graduated plexiglass retention boards. s of the camera before placing the boards in the camera. 17. Initial readings of the height of the curls are taken before placing the boards in the chamber. These readings are called Li. 18. The boards are placed in the chamber and the door is closed. The camera will not open until the test is over. 19. The heights of the curls are recorded at specific time intervals. These readings are called with Lt. The time intervals are 15, 30 minutes, 1, 1-1 / 2, 2, 3, 4, 6 hours or more, if necessary. NOTE: For Spritz, gel and mousse, the data is recorded until after 4 hours. For selection purposes, 90 minutes can be used; for decision making purposes, four (4) hours are preferred. C. Product Application Product Quantity to Apply Hair spray in two (2) sprays spray applied evenly on both the front and the back of the curled lock at a distance of 8"Sprays for hair with two ( 2) spray applied pump or spray evenly on both the front and the back of the curly strand at a distance of 8"Spritz Type Products Two (2) sprays applied evenly on both the front and the back of the curled lock to a distance of 8"Gels 0.50 grams of the product is applied to wet hair and combed well to distribute evenly. Then the hair is curled on a curler in the specified manner and dried in an oven at 100 ° C for 1 hour, then at room temperature overnight on a flat surface. Mousse 0.50 grams of the product is applied to dry hair and combed well to distribute evenly. Then the hair is curled on a curler in the specified manner and dried in an oven at 100 ° C for 1 hour, then at room temperature overnight on a flat surface.

D. Calculations 1. The curl retention percentage is calculated as follows:% curl retention = (Lo) - (Lt) X 100 (Lo) - (Li) Where: Lo = fully extended hair length Li = hair length before exposure (initial) Lt = hair length after exposure. 2. A Lotus 123 program is used to enter the data and plot. E. References The Aerosol Handbook, Montfort A. Johnson, "High Humidity Curl Retention Testing," p. 432. 3. DRYING TIME AND ADHESIVITY / PEGAJOSITY OF THE HAIR DEVICES (TRAINED PANEL METHOD) As the solvent evaporates from the newly applied hair spray, the formulation undergoes a period during which it is sticky to the touch . This effect is due to the plasticizing action of the solvent and is influenced by a number of factors. Among these are the heaviness of the spray, the temperature, the air movement, the intrinsic tendency of a formulation towards adhesiveness and its tendency to retain the solvent. In this test, the first three factors are controlled by determining the tack time and total drying of a formulation.

EQUIPMENT: 3-1 / 2 strands of hair (virgin European brown hair) cut to a length of 6-1 / 2"Laboratory stopwatch or clock - Prototype pump or atomizer or spray for testing PROCEDURE: ( 3 to 5 replications are usually run.) 1. Suspend the lock of hair vertically on a plate 2. Apply controlled amount of product to the lock of hair at a distance of 8". For pump or atomizer systems two (2) sprays are applied to the front of the strand. For aerosols, two (2) two-second sprays are applied to the front of the strand. 3. The stopwatch is activated and the participants are allowed to evaluate the strands. 4. The full length of the strands is felt with the hands and indicated when the hair begins to become sticky / adhesive, (b) is no longer adhesive / sticky and (c) is completely dry. 5. The total drying time and the duration of the stickiness period, therefore, can be determined for the test and control samples. NOTE: To minimize the tendencies to the right hand, the hands alternate when the samples are evaluated. REPORT: An average of 3 to 5 evaluations per sample. 4. INITIAL CURL FALL The amount of hair curling after spraying is measured to simulate a consumer's actual experience when he sprays his hair and the actual loss of hairstyle maintenance that takes place after it dries. EQUIPMENT / MATERIALS: 1. Hair strands (length: 6.5, weight: 2 grams) wound in a spiral. 2. Pins. 3. Stopwatch or laboratory clock. 4. Curlers - 5/8"outside diameter 5. Tuft plate with 1/4" lines. HAIR PREPARATION: 1. All hair is washed well and while wet it is wound in a diagonal spiral on a 5/8"curling iron, and secured with pins at each end Note: Spirals should not overlap, but should Cover all the curler. 2. The locks are dried overnight or placed in an oven at 45 ° C for one (1) hour or placed under a salon dryer for one (1) hour. 3. Before spraying the hair, the curling irons are carefully removed, trying to keep the hair as close together as possible. 4. Then the strands are sprayed with the product and the curling drop is measured every minute for ten (10) minutes. 5. The application is determined using the following chart: Type of spray for the Distance given the Quantity of product applied to the horse pump Pump 8"4 pressures - only to the front Aerosol 8" 4 seconds - only to the front 6. Ideal conditions should be 70 ° F and 50% relative humidity. Six (6) strands are tested for each variable and the data are statistically compared using the following formula: 1 - lo - lf x 100 lo - li lo = original length, hair completely extended li = initial length of the cairel, before drying lf = final length of the cairel, after drying Since the present invention has been described with particular reference to certain modalities thereof, it should be understood that the technicians in the material could make changes and modifications that are within the scope of it. Accordingly, it is intended to adhere to the following claims. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as an antecedent, what is contained in the following is claimed as property.

Claims (17)

1. CLAIMS 1. A hair spray composition containing 80% or less of VOC, characterized in that it comprises, by weight: (a) about 0.5 to 12% of a copolymer of ethyl ester or maleic anhydride butyl ester and methyl vinyl ether , which is prepared. (i) by copolymerization of the monomers in a solvent by free radical polymerization, at a temperature of about 60 to about 90 ° C, in the presence of about 0.05 to about 10% by weight with respect to the maleic anhydride monomer, a polymerization initiator whose decomposition fragments are soluble in a hydroalcoholic composition with 55% VOC, and (ii) the copolymer composition is esterified, wherein the copolymer is transparent and has an average molecular weight of from about 30,000 to about 120,000, a polydispersity less than about 2.5 and a specific viscosity of about 0.25 to 0.39, optionally neutralized in an amount of up to 25 mol%, (b) from 0 to 80% ethanol, (c) from 19 to 99% water, and (d) from 0 to 35% propellant, wherein the composition has a transparent appearance, has a Brookfield viscosity less than about 30 cps at a level of 5% solids, and forms transparent films that have high moisture hold curl (maintenance) of at least about 90%, a tack time less than about 30 seconds and a shorter drying time about 45 seconds, and which forms dew particles less than about 100 μm in a pump or atomizer system, and less than about 80 μm in an aerosol system. 2. A hair spray composition according to claim 1, characterized in that the copolymer has an average molecular weight of about 50,000 to about 100,000 and a polydispersity of about 1.8 to about 2.
2. 2.
3. 3. A hair spray composition according to claim 2, characterized in that the average molecular weight is from about 60,000 to about 80,000.
4. 4. A hair spray composition of pump system or atomizer according to claim 1, characterized in that it does not contain propellant.
5. 5. A hair spray composition of an aerosol system according to claim 1, characterized in that it contains a propellant.
6. 6. A hair spray composition according to claim 1, characterized in that the copolymer is an ethylhemister copolymer.
7. 7. A hair spray composition according to claim 1, characterized in that the copolymer is included therein in the form of a 50% ethanolic solution of copolymer.
8. 8. A hair spray composition according to claim 1, characterized in that the copolymer is neutralized in an amount of up to about 25 mol%.
9. 9. A hair spray composition according to claim 1, characterized in that the polymerization initiator is present in an amount of about 1 to about 5% by weight with respect to the maleic anhydride monomer, using an azo initiator having a half-life of 10 hours from about 60 to about 70 ° C.
10. 10. A hair spray composition according to claim 1, characterized in that the polymerization initiator is an azobis compound having a water solubility of 0.5 g / 100 g of water.
11. 11. A hair spray composition according to claim 10, characterized in that the azobis compound is selected from the group consisting of 1,1'-azobis (1-cyclohexanecarbonitrile); 2, 2'-azobis dihydrochloride (N, N'-dimethylene isobutyramidine); 2,2'-dihydrochloride-azobis (2, amidinopropane); 2, 2 '-azobis (N, N' -dimethylene-isobutylamidine); 4, '-azobis (4-cyanopentanoic acid); 2,2'-azobis. { 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroethyl-3-propionamide}; 2,2'-azobis'2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] -propionamide}; 2, 2'-azobis [2-methyl-N- (2-hydroxyethyl)] -propionamide; and 2,2'-azobis diisocyte (isobutyramide).
12. 12. A hair spray composition according to claim 11, characterized in that the azobis compound is 4,4'-azobis (4-cyanopentanoic acid).
13. 13. A hair spray composition according to claim 1, characterized in that it is an aerosol system containing a can corrosion inhibitor.
14. 14. A hair spray composition according to claim 1, characterized in that it contains ethanol in an amount of up to 55%.
15. 15. A hair spray composition according to claim 6, characterized in that the specific viscosity of the copolymer is from about 0.28 to about 0.35 in the form of a 1% solution of the copolymer in ethanol.
16. 16. A hair spray composition according to claim 1, characterized in that the VOC level is 55% or less.
17. 17. A hair spray composition according to claim 1, characterized in that the esterification of the copolymer is carried out in the absence of an esterification catalyst.